This study aimed to evaluate the effect of gamma irradiation (GI) on the physicochemical, technological, antioxidant and microbiological characteristics of different whole sorghum flours (WSF), as well as to characterize the profile of chemical constituents by paper spray mass spectrometry (PS-MS). The doses applied interfered in the staining characteristics of the evaluated flours, providing the darkening of the same. For the other physicochemical, technological, and antioxidant parameters, no significant influence of the process was observed. The fingerprint obtained in both ionization modes had not been influenced by irradiation, being flavonoids, phenylpropanoids, amino acids, benzoic acid derivatives, carboxylic acids, and sugars tentatively identified. In microbiological terms, there was a reduction of molds, yeasts, and Bacillus cereus in irradiated WSF compared to control (non-irradiated). Therefore, the application of low doses of gamma irradiation represents an advantageous alternative for the conservation of WSF and maintenance of bioactive compounds identified by the PS-MS technique.

The pequi pericarp corresponds to the largest portion of the fruit and has a high nutritional value, but it is discarded as an agro-industrial residue. The present study aimed to prepare and characterize flours from the pequi pericarp in terms of their proximate composition, its antioxidant potential before and after the in vitro digestibility process and chemical profile, aiming at the full use of this fruit. The samples of pequi pericarp flours from the cities of Sete Lagoas, Paraopeba and Felixlândia were analyzed. The profile of chemical compounds present in the flours was determined using paper spray mass spectrometry. The in vitro simulated digestion technique was used to verify the stability of the phenolic compounds and the maintenance of the antioxidant capacity of the samples. The flours from the pequi pericarp showed to have higher levels of protein, ash and dietary fiber, compared to the data described in the literature for the pulp of the fruit. The analysis of paper spray mass spectrometry allowed the identification of 46 chemical compounds including amino acids, sugars, organic acids and phenolic compounds. The analysis of the main components showed that there was no chemical variation among the fruits from the cities studied. Through the in vitro digestibility technique, it was possible to observe an increase in the bioaccessibility of phenolic compounds, contributing to increase the already significant antioxidant capacity of the samples. It was concluded that the pequi pericarp flour has the potential to be used as a food ingredient due to the high bioaccessibility of its bioactive compounds, capable of reducing the risk of developing diseases caused by oxidative stress.

This study involved an animal experiment in which testosterone propionate was intramuscularly injected into four steers, and the ensuing urine samples were analyzed using high-performance liquid chromatography-tandem mass spectrometry. The enzymatic hydrolysis conditions were analyzed using analysis of variance (ANOVA) and response surface methodology employing a 33 Box-Behnken design. A survey study was performed in which 48 urine samples were collected from eight untreated steers to estimate the endogenous levels of testosterone metabolites, and it was found that 17β-testosterone was not detected in the majority of the samples, whereas 17α-testosterone was present in 43 of the 48. Drug abuse was identified within 11 days of 17β-testosterone administration. The ratio between both isomers was also assessed; however, a cut-off limit based on an untreated population could not be estimated due to the absence of the beta isomer. Therefore, there may be a correlation between the exogenous use of testosterone in castrate animals and high levels of 17β-testosterone, although confirmation through further investigation would be required.

One of the recurrent problems of the agroindustry sector is the incorrect disposal of waste because of the complexity of the material, moisture, among other factors. Waste is not used in tonnage, but is systematically used. Examples of residues are malt bagasse and cassava peel, produced in large quantities in the brewing industry and flour production, respectively. In this context, the objective of this study was to evaluate bioactive compounds of flours produced from agroindustry waste to potentiate their use as an ingredient rich in antioxidants. The flours produced from agroindustry waste were evaluated for phenolic compounds, total carotenoids, antioxidant activity, and the attainment of phenolic profiles and fingerprints by paper spray mass spectrometry. It was possible to identify a broad class of compounds in both flours, such as phenolic acids, flavonoids, among others. The flours can be possibly included in food commodities or packaging formulation since they are natural antioxidants, thus adding value to these products and reducing environmental issues. However, further analysis is needed to ensure bioavailability as well as food safety.

Green Cavendish banana peel and pulp flours were obtained by three drying methods: oven dryer at 70 °C; air fryer at 180 °C and domestic oven at 180 °C, being the latter two new possibilities. Bioactive constituents using paper spray ionization mass spectrometry (PS-MS), phenolic identification and quantification by ultra-performance liquid chromatography with UV-Visible detection (UPLC/UV-Vis) and antioxidant capacity were evaluated. Phenolic acids showed distinct thermal stability between the treatments. Gallic acid was the predominant compound, ranging from (29.56 to 1211.74 mg 100 g-1) and had higher concentration than that found in other bananas described in literature. Green Cavendish banana flour is an advantageous source of bioactive compounds and antioxidant capacity, especially its peel. 26 compounds were identified by PS-MS: phenolics, organic acids, sugars, amino acid, phytosterol, iridoid and coumarin derivatives. Green Cavendish banana flour has great functional potential, and the air fryer can be a promising alternative for drying.

The incorporation of Cerrado fruits in food products such as ice cream has many advantages because it represents a source of nutrients and bioactive compounds. Given the demand for less laborious methods to analyze food, the paper spray ionization mass spectrometry technique was applied for the first time for a rapid characterization of the chemical components found cagaita ice cream. PS-MS in positive and negative ionization modes were used. The profile of volatile compounds was determined by headspace solid-phase microextraction combined with gas chromatography-mass spectrometry. Fingerprints obtained through PS-MS identified various classes of compounds, such as flavones, anthocyanins, sugars, organic acids, hydroxybenzoic acids, fatty acids, hydroxycinnamic acids, lignin, and phenylpropanoid. The use of both fibers enabled the extraction and identification of 18 volatile compounds in cagaita, and 16 of them were also identified in cagaita ice cream. The most common volatile compound found in both cagaita and ice cream was 3-carene monoterpene. Considering the effect of processing on cagaita constituents, 89% of the volatile compounds remained in the ice cream. Also, 78% of the fruit chemical compounds analyzed by PS-MS were found in the product. Thus, the results indicate that most of the fruit compounds remained in the ice cream after processing.

RESUMO Determinou-se a composição do perfil volátil de frutos de cambuizeiro (Myrciaria floribunda) utilizando-se microextração em fase sólida no modo headspace e cromatografia gasosa acoplada a espectrometria de massas. As fibras PA (polyacrylate) e DVB/CAR/PDMS (divinylbenzene/carboxen/polydimethylsiloxane) foram otimizadas quanto aos parâmetros de extração (agitação, tempo e temperatura de extração), a fim de selecionar a fibra com maior número de compostos isolados. Um total de 48 compostos voláteis foram identificados através do HS-SPME / GC-MS presentes nos frutos maduros de cambuí. Os compostos voláteis foram classificados em cinco classes químicas, sendo a maioria pertencente à classe dos sesquiterpenos (71 %). Além disso, foi possível verificar que a fibra revestida com poliacrilato (PA) teve melhor desempenho, permitindo a extração de um maior número de compostos voláteis (n = 35). As condições de extração que permitiram o isolamento de um maior número de compostos voláteis, corresponderam a tempos superiores de 26 min e temperaturas acima de 85 °C com agitação de 79 rpm, isto para a fibra PA. Da mesma forma, verificou-se que os sesquiterpenos hidrocarbonetos foi a classe química mais presente nos frutos, o que está relacionado principalmente ao perfil volátil dos frutos de cambuí.

ABSTRACT The composition of the volatile profile of rumberry fruits (Myrciaria floribunda) was determined using solid- phase microextraction in headspace mode and gas chromatography, coupled with mass spectrometry. The PA (polyacrylate) and DVB/CAR/PDMS (divinylbenzene/carboxen/polydimethylsiloxane) fibers were optimized for the extraction parameters (agitation, extraction time and temperature), in order to select the fiber with the highest number of isolated compounds. A total of 48 volatile compounds were identified using HS-SPME/GC-MS present in the ripe fruits of rumberry. The volatile compounds were classified into five chemical classes, the majority belonging to the sesquiterpenes class (71%). In addition, it was possible to verify that the fiber coated with polyacrylate (PA) had better performance, allowing for the extraction of a greater number of volatile compounds (n = 35). The extraction conditions that allowed the isolation of a greater number of volatile compounds corresponded to times greater than 26 minutes and temperatures above 85 °C, with agitation of 79 rpm for the PA fiber. Likewise, it was found that the hydrocarbon sesquiterpenes was the chemical class most present in the fruits, which is mainly related to the volatile profile of rumberry fruits.

RESUMO OBJETIVO: Radiação ionizante pode causar alterações no metaboloma celular devido à quebra de ligações no DNA. O objetivo deste trabalho foi evidenciar a resposta aguda tecidual induzida pela exposição da radiação ionizante. MÉTODOS: Análises histológicas foram realizadas nos órgãos extraídos de ratos para análise de alterações microscópicas. As lâminas histológicas coradas com hematoxilina eosina (HE) foram analisadas em aumento (40x). Posteriormente, os tecidos foram submetidos a espectrometria de massa, que permitiu análise molecular e o Desi-MSI que gerou imagem molecular de lipídios, identificando alterações na intensidade, principalmente no cérebro. RESULTADOS: As análises histológicas encontraram alterações inflamatórias inespecíficas, nem áreas de fibrose, necrose ou apoptose, sugerindo ausência de alterações morfológicas. As imagens de lipídios cerebrais obtidas por Desi-MSI permitiram observar as inúmeras alterações na intensidade nas seções teciduais do encéfalo. CONCLUSÕES: Alterações agudas radioinduzidas de massa do órgão e histológicas nos órgãos dos ratos expostos não puderam ser observadas a 5 Gy. Entretanto, mudanças em nível molecular foram observadas nas imagens de Desi-MSI dos lipídios cerebrais. O método Desi-MSI mostrou-se eficiente e relevante, permitindo a análise molecular regi-onal dos tecidos no SNC, expandindo um novo campo de estudo que ainda está em sua infância: a radiometaboloma.

SUMMARY OBJECTIVE: Ionizing radiation can cause radio-induced changes in the cellular metabolome due to the breakdown of DNA bonds. Our goal was to find the early tissue response to radiation exposure supported by distinct analytical methods. METHODS: Histological analyses were performed on the organs extracted from rats to search for microscopic changes. The histological slides stained with hematoxyline-eosin (HE) were analyzed in magnification (40x). Subsequently, the tissues were subjected to mass spectrometry that allowed molecular analysis and DESI-MSI that generated the molecular image of lipids, assessing changes in intensities, especially in the brain. RESULTS: The histological analysis found nonspecific inflammatory changes; no areas of fibrosis, necrosis, or apoptosis were identified, suggesting non-morphological tissue alterations. However, the DESI-MSI images of brain lipids allowed the observation of many radio-induced changes in the lipid's intensities. CONCLUSIONS: No early radio induced histological or mass weight changes in the radiation exposed rats could be observed at 5 Gy. However, early changes in the molecular level were observed in the DESI-MSI images of the brain lipids. The DESI-MSI method proved to be efficient and relevant, allowing a regional molecular analysis of the tissues, expanding a new field of study that is still in its infancy: radiometabolomics.

Much is said and written regarding alchemy all across the world, in what could be called a renaissance of alchemical studies. However, relatively little is done in terms of actual alchemical laboratory work. The aim of the project described herein was to show how crucial the development of technical alchemical practice was along the centuries, in the discovery of an immense number of substances, processes and operations, which were of paramount importance in the establishment of modern chemistry. Alchemy is often derided in many circles. On the contrary, for two thousand years it constituted the basis of humankind’s understanding of the material world and the changes undergone by compounds and materials. Here we present an experimental reconstitution of several alchemical discoveries of great importance, using old descriptions followed by modern characterizations. The results were often startling and demonstrated how ancient wisdom bore fruit in different ways, even in the absence of our present-day means of analysis.

In this work, the peels of ripe banana (Musa sp.), variety “Prata”, were used to prepare a flour, which was evaluated for its physicochemical characteristics and antioxidant activity. The characterization of its chemical profile was performed by a fast and simple method: paper spray-mass spectrometry. This flour had high carbohydrate content and total dietary fiber, and significant amount of total phenolic compounds with antioxidant activity. In addition, this flour exhibited higher water-holding, oil-holding and swelling capacities than those of fruit by-products reported in the literature. Fourier-transform infrared spectroscopy confirmed the presence of functional groups of cellulose, hemicellulose, and lignin, constituents of insoluble dietary fiber. By the paper spray-mass spectrometry technique, it was possible to suggest the presence of 26 substances such as organic acids, phenolic acids, flavonoids, sugars, quinones, and terpenoids. Thus, this study demonstrated that the ripe banana peel flour has potential application as an ingredient for functional foods.

The use of sorghum in human nutrition has been expanded due to its nutritional composition and its functional potential. Extrusion has been used to improve the quality of sorghum. The aim of this work was to assess the effect of extrusion in the nutritional composition, phenolic compounds content of two sorghum, and characterize the profile of chemical constituents by paper spray mass spectrometry (PS-MS). Extrusion increased the carbohydrate and fiber contents and reduced moisture, lipids and ashes, and enabling a higher degree of liberation of phenolic compounds and antioxidant activity. The fingerprint obtained in both ionization modes had been influenced by extrusion, allowing for a greater compounds’ identification on the extruded samples. The analysis of sorghum samples’ main components made distinguishing of the main constituents possible, as well as highlighted the extrusion effect and the influence of the genotypes. This study demonstrated that extrusion enabling a higher liberation of phenolic compounds, which were identified by the PS-MS technique.

The objective of this work was to determine the chemical composition, total phenolic compounds content, antioxidant capacity through the ABTS (2,20-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) method, as well as to evaluate the use of paper spray ionization mass spectrometry (PS-MS) to obtain fingerprints in different brands of mixed industrialized beverage based on fruits and vegetables with “detox” denomination. The carbohydrate contents ranged from 4.17% (sample D) to 12.72% (sample G). The differences may be related to the composition and proportion of the ingredients present in each formulation. The contents of total phenolic compounds varied between 26.75 mg GAE (gallic acid equivalents) g-1 (sample F) to 48.61 mg GAE g-1 (sample D). The samples A, B and C contain cabbage, spinach and parsley and presented significantly higher phenolic compounds content than the other samples. The antioxidant activity values varied between 1.76 µmol L-1 Trolox g-1 (sample B) to 18.95 µmol L-1 Trolox g-1 (sample E). The brands E, F, and G, that presented higher antioxidant potential, have ingredients pineapple, apple, cabbage, and ginger as common. The analysis of PS-MS allowed for the identification of a number of substances, including organic acids, sugars, and phenolic acids. PS-MS is a relatively simple method, fast and efficient to obtain fingerprints of mixed beverages.

Desorption electrospray ionization mass spectrometry imaging (DESI-MSI) was used to assess the spatial distribution of some key flavonoids in peppermint (Mentha × piperita L.) leaves. The chemical images were generated by applying DESI-MSI on the peppermint leaves imprinting while acquiring the spectra in the negative ion mode. The following key flavonoids were detected and grouped within well-known biosynthetic routes in plants: naringenin route [naringenin, sakuranetin, hesperetin, hesperidin, luteolin, and apigenin]; luteolin route [luteolin, chrysoeriol, luteolin-7-O-D-glucuronide, luteolin-7-O-D-glucoside, luteolin-7-O-neohesperidoside]; apigenin route [apigenin, apigenin-7-O-gentiobioside, apigenin-7-O-neohesperidoside, thymusin/pilosin, pebrellin, acacetin/genkwanin, ladanein, xanthomicrol/pedunculin/nevadensin]. Maps of the spatial distribution of these flavonoids throughout the peppermint leaves within each route were then displayed. The results described herein comprise an important (although still underexplored) subject that certainly will experience a remarkable growth in the next years.

Cagaita is a fruit from Brazilian cerrado, belongs to Myrtaceae family, and has important economic value. This work aimed to determine the total antioxidant capacity (extractable and non-extractable fractions) by different methods and to evaluate the use of paper spray mass spectrometry to obtain fingerprints of cagaita from different regions with the aid of principal components analysis. Cagaitas had higher antioxidant activity than those found in other fruits mentioned in literature, and the non-extractable fraction was 18.90 to 21.05% of the antioxidant capacity. The analysis of paper spray mass spectrometry in positive and negative ionization modes identified several substances, including organic acids, sugars, amino acids and several other classes of phenolic compounds. Analysis of the main components of cagaita samples permitted discrimination of the major constituents such as sugars and different kinds of phenolic compounds. Thus, this study demonstrated that paper spray mass spectrometry is a simple and ultrafast method with minimum sample preparation that allows the analysis of the chemical profile of cagaita.

The objective of this study was to explore the extraction and identification of volatile organic compounds (VOCs) present in cagaita fruit (Eugenia dysenterica). Parameters such as type of extraction fiber, agitation, extraction time and extraction temperature were investigated. Initially, the VOCs were extracted using headspace solid-phase microextraction. Then, the compounds were identified using gas chromatography coupled to mass spectrometry. Results revealed the presence of at least 26 different compounds and the polyacrylate (PA) fiber promoted the extraction of a larger number of VOCs. Regarding the PA fiber, the most efficient extraction was achieved using a 50 rpm agitation at 45 ºC for 30 min. The majority were monoterpenes (34.64%) and esters (36.28%). An increase in the extraction temperature promoted the isolation of more VOCs when using carboxen/polydimethylsiloxane (CAR/PDMS) and divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fibers. However, these fibers allowed the isolation of a smaller number of VOCs. The extraction time and agitation had no significant influence.